JP6813809B2 - Composition for film formation and method for producing the same - Google Patents

Description

The present invention relates to a film-forming composition and a method for producing the same, and more specifically, a film-forming cloth containing a hydrolyzable condensate of hydrolyzable silane and inorganic fine particles to which an amphipathic organosilicon compound is bonded. The present invention relates to a composition and a method for producing the same.

So far, various attempts have been made to improve the functionality of polymer compounds. For example, as a method for increasing the refractive index of a polymer compound, an aromatic ring, a halogen atom, and a sulfur atom have been introduced. Among them, episulfide polymer compounds and thiourethane polymer compounds into which sulfur atoms have been introduced have been put into practical use as high refractive index lenses for eyeglasses.

However, since it is difficult to design a material having a refractive index exceeding 1.7 with a polymer alone, a method using inorganic fine particles is known as the most promising method capable of achieving a higher refractive index.

This method is a method of mixing a polymer and inorganic fine particles to achieve a high refractive index. As a mixing method, a method of mixing a polymer solution and a dispersion of inorganic fine particles is common, and in this case, the polymer plays a role as a binder that stabilizes the dispersion of the inorganic fine particles without breaking the dispersion.

It has been reported that a hydrolyzable condensate of hydrolyzable silane or polyimide can be used as the binder polymer. For example, a method of increasing the refractive index by using a hybrid material obtained by mixing a hydrolyzed condensate of alkoxysilane and an inorganic oxide dispersion material in which zirconia or titania is dispersed has been reported (see Patent Document 1). .. Further, a method of increasing the refractive index by using a hybrid material in which polyimide and titania, zinc sulfide, etc. are dispersed has been reported (see Patent Document 2).

Although these hybrid materials have been devised in various ways to increase the refractive index, they can be produced as a composition in a high refractive index region having a refractive index exceeding 1.7 and having a film thickness exceeding 1 μm. The present situation is that no suitable composition has been realized, and further, the storage stability of the coating composition has not been studied.

By the way, in recent years, when developing electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging devices, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs). In addition, high-performance hybrid materials have been required.

Specific properties required include heat resistance, transparency, high refractive index, thick film, crack resistance, storage stability of the coating composition, and the like.

When a hydrolyzable condensate of hydrolyzable silane, that is, polysiloxane and inorganic fine particles are mixed, a film having high heat resistance and transparency is generally obtained. Here, when the refractive index is improved, it is common to decrease the content of polysiloxane having a low refractive index and increase the content of inorganic fine particles having a high refractive index. When increasing the film thickness, it is common to increase the solid content concentration of the coating composition containing the polysiloxane and the inorganic fine particles.

The method of realizing the increase in film thickness by increasing the solid content concentration of the coating composition is to increase the viscosity of the coating composition by increasing the solid content concentration, and the film produced from the highly viscous coating composition is a thick film. It is caused by becoming. This technique applies to organic polymers such as acrylic polymers.

However, in a coating composition containing polysiloxane and inorganic fine particles, the viscosity of the composition does not easily increase even if the solid content concentration is increased, that is, a film is formed with a low viscosity, so that it is difficult to thicken the film. Further, if an attempt is made to increase the refractive index of the composition at the same time as thickening the film, the content of inorganic fine particles in the coating composition increases as described above in order to improve the refractive index, and the viscosity of the coating composition is further increased. It becomes difficult to change. This is because the inorganic fine particles selected for the coating composition in the field are present in a highly dispersed state in the coating composition, and the highly dispersible inorganic fine particles have a characteristic that it is difficult to increase the viscosity. by.

Thickening of the composition containing the hydrolyzable condensate of hydrolyzable silane and the inorganic fine particles may be possible by increasing the viscosity of the coating composition by increasing the dispersed particle size of the inorganic fine particles. ..

However, although thickening can be achieved by this method, there is a problem that the storage stability of the coating composition deteriorates, and the life of the product cannot be guaranteed. A coating composition having poor storage stability may have a problem that, for example, an increase in the viscosity of the coating composition cannot be suppressed during storage, the target film thickness cannot be controlled, or the coating composition gels and cannot be used.

As described above, there is a technical trade-off between achieving a thick film of the composition containing the polysiloxane and the inorganic fine particles and achieving good storage stability.

As described above, in the composition containing polysiloxane and inorganic fine particles, the composition has high heat resistance and transparency, can be thickened while exhibiting a high refractive index, has crack resistance, and has excellent storage stability. There are no reports of the coating composition and the method for producing the same.

JP-A-2007-246877 Japanese Unexamined Patent Publication No. 2001-354853

The present invention has been made in view of such circumstances, and exhibits high heat resistance and transparency and a high refractive index in a coating composition containing a hydrolyzable condensate of hydrolyzable silane and inorganic fine particles. At the same time, it is an object of the present invention to provide a film-forming composition which can be thickened and has excellent storage stability of the coating composition and a method for producing the same.

The inventors of the present application have found that a composition containing a hydrolyzable condensate of hydrolyzable silane and inorganic fine particles subjected to a special dispersion treatment is suitable as a film-forming composition for producing an electronic device. , The invention of the present application has been completed.

That is, the invention of the present application
1. 1. (A) Component: The following formula (1)

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
A hydrolyzate condensate of at least one hydrophilic silane represented by, and a component (B): a metal oxide colloidal particle (B1) having a primary particle diameter of 2 to 60 nm as a nucleus, and the surface thereof is 1 to 1. Poly as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating (B2) composed of metal oxide colloidal particles having a primary particle size of 4 nm. It has one or more poly (oxyalkylene) groups selected from oxyethylene group, polyoxypropylene group or polyoxybutylene group, and is selected from alkylene group or vinylene group having 1 to 18 carbon atoms as a hydrophobic group. A film-forming composition containing inorganic fine particles to which an amphoteric organic silicon compound having one or more groups is bonded.
2. 2. The film-forming composition according to 1, wherein R ² in the formula (1) is a methyl group, an ethyl group, a phenyl group, a biphenyl group or a phenanthryl group, and a is 1.
3. 3. The film-forming composition according to 1 or 2, wherein the amphipathic organosilicon compound is a compound in which the number of moles of the oxyalkylene group added in the hydrophilic group is 3 to 40 mol.
4. The amphoteric organic silicon compound bonded to the surface of the modified metal oxide colloidal particles (B3) of the component (B) is 3 to 3 to the total metal oxide of the modified metal oxide colloidal particles (B3). The film-forming composition according to any one of 1 to 3, which is bonded at a mass ratio of 30% by mass.
5. The group in which the metal oxide colloidal particles (B1) of the component (B) are composed of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. The film-forming composition according to any one of 1 to 4, which is an oxide of at least one metal selected from the above.
6. Any one of 1 to 5 in which the coating material (B2) of the component (B) is an oxide of at least one metal selected from the group consisting of Si, Al, Sn, Zr, Mo, Sb and W. The film-forming composition according to
7. (A) Component: The following formula (1)

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
Hydrolyzed condensate of at least one hydrophilic silane represented by and component (B): Metal oxide colloidal particles (B1) having a primary particle diameter of 2 to 60 nm are used as nuclei, and the surface thereof is 1 to 4 nm. Polyoxy as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating (B2) composed of metal oxide colloidal particles having a primary particle size. It has one or more poly (oxyalkylene) groups selected from an ethylene group, a polyoxypropylene group or a polyoxybutylene group, and is selected from an alkylene group having 1 to 18 carbon atoms or a vinylene group as a hydrophobic group. A method for producing a film-forming composition, which comprises a step of mixing with inorganic fine particles to which an amphoteric organic silicon compound having one or more groups is bonded.
8. The method for producing a film-forming composition according to 7, wherein R ² in the formula (1) is a methyl group, an ethyl group, a phenyl group, a biphenyl group or a phenanthryl group, and a is 1.
9. The method for producing a film-forming composition according to 7 or 8, wherein the amphipathic organosilicon compound is a compound in which the number of moles of the oxyalkylene group added in the hydrophilic group is 3 to 40 mol.
10. The production of the film-forming composition according to any one of 7 to 9, which comprises a step of mixing the component (A) and the component (B) and then heating at 23 ° C. or higher and 150 ° C. or lower. Method,
A coating film obtained from the coating film forming composition according to any one of 11.1 to 6.
12. An electronic device comprising a base material and a coating film according to 11 formed on the base material.
13. An optical member comprising a base material and the coating film according to 11 formed on the base material.
A solid-state imaging device or charge-binding device having a complementary metal oxide semiconductor, comprising at least one film according to 14.11.
An implant material, a flattening material, or a microlens material for a solid-state image sensor, which comprises at least one layer of the coating film according to 15.11.
I will provide a.

According to the invention of the present application, the component (A): the following formula (1)

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
Hydrolyzed condensate of at least one hydrophilic silane represented by and component (B): Metal oxide colloidal particles (B1) having a primary particle diameter of 2 to 60 nm are used as nuclei, and the surface thereof is 1 to 4 nm. Polyoxy as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating (B2) composed of metal oxide colloidal particles having a primary particle size. It has one or more poly (oxyalkylene) groups selected from an ethylene group, a polyoxypropylene group or a polyoxybutylene group, and is selected from an alkylene group having 1 to 18 carbon atoms or a vinylene group as a hydrophobic group. When a film is formed from a film-forming composition obtained by mixing inorganic fine particles to which an amphoteric organic silicon compound having one or more groups is bonded, a film having high heat resistance and transparency is obtained, and electrons are obtained. Long-term reliability can be improved when mounted on a device.

Further, in order to obtain a film having a high refractive index, inorganic fine particles having a high refractive index (component (component)) which has been subjected to a special dispersion treatment than a hydrolyzable condensate of hydrolyzable silane having a low refractive index (component (A)). By using a film-forming composition having an increased content of B)), the viscosity of the composition is increased and a thick film can be formed. The obtained film-forming composition has good storage stability, and the obtained film exhibits high refractive index and high transparency.

According to the present invention, the composition containing the component (A) and the component (B) has high heat resistance and transparency, can be thickened while exhibiting a high refractive index, and has crack resistance. It is possible to provide a film-forming composition capable of forming a certain film and having excellent storage stability.

The range of the refractive index of the film obtained from the film-forming composition of the present invention depends on the usage situation, but the lower limit is preferably 1.70 or more, more preferably 1.75 or more, still more preferably 1. .80 or more. The upper limit is not particularly limited, but is 2.00 or less, or 1.95 or less. As the definition of high refractive index in the present invention, 1.70 or more is referred to as high refractive index at a wavelength of 550 nm.

The film-forming composition of the present invention can have a higher viscosity than a conventional composition containing a hydrolyzable condensate of hydrolyzable silane and inorganic fine particles, and thus can be thickened. For example, a thick film can be obtained without using the spin coating method twice or a complicated spin recipe, and the process margin is wide.

Since the film-forming composition of the present invention retains a high degree of dispersibility of the inorganic fine particles, the film-forming composition has good storage stability, and the viscosity rapidly increases and gels during storage. As a result, the life of the product is long, and as a result, the cost can be reduced.

Further, in the film-forming composition of the present invention, the film thickness, the refractive index, and the transmittance can be controlled by changing the type of the hydrolyzable condensate of the hydrolyzable silane or changing the addition amount thereof.

The coating film produced by using the coating film forming composition of the present invention having the above characteristics includes a liquid crystal display, an organic electroluminescence (OLED) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film transistor, and the like. It can be suitably used as a member for manufacturing electronic devices such as dye-sensitized solar cells and organic thin film transistors (TFTs). Further, it can be suitably used as a lens member for which a high refractive index is required. Embedded films and flattening films on photodiodes, flattening films before and after color filters, microlenses, flattening films and conformal films on microlenses, which are members of solid-state image sensors for which high refractive index is particularly required. Can be suitably used as.

Hereinafter, the present invention will be described in more detail.

<Ingredient (A)>
The hydrolyzable condensate of the hydrolyzable silane of the component (A) contained in the film-forming composition of the present invention is the following formula (1).

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
In the hydrolyzate of at least one hydrolyzable silane represented by, the silanol groups are dehydrated and condensed to form a polysiloxane.

In the above formula (1), examples of the alkyl group of R ¹ include alkyl groups having 1 to 6 carbon atoms, which have linear, branched, or cyclic alkyl moieties, such as methyl group and ethyl group. , N-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-Methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group , N-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n- Butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3 -Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2, -trimethyl-n- Examples thereof include a propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.

In the above formula (1), the alkyl group having 1 to 18 carbon atoms of R ² has a linear, branched, or cyclic alkyl moiety, and has a methyl group, an ethyl group, an n-propyl group, and an isopropyl. Group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl Group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1 -Methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2- Dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group , 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2,-trimethyl-n-propyl group, 1-ethyl- 1-Methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Examples thereof include a group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

Further, in the above formula (1), examples of the aryl group having 6 to 18 carbon atoms of R ² include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group and a cyclohexyl group.

The hydrolyzable silane represented by the formula (1) is, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, or methyltri. Ethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isobutyltriethoxysilane, t-butyltriethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, fe. Examples thereof include, but are not limited to, nantriltrimethoxysilane, biphenyltrimethoxysilane, and dimethoxydimethylsilane.

In the hydrolyzable condensate of the hydrolyzable silane of the component (A), other hydrolyzable silanes having a halogen atom as a hydrolyzing group such as tetrachlorosilane together with the hydrolyzable silane represented by the above formula (1). Compounds may be used.

In the formula, in the formula of R ² , a represents an integer of 0 to 3, that is, the hydrolyzable condensate of the hydrolyzable silane represented by the formula (1) is a tetrafunctional, trifunctional or bifunctional poly. Indicates siloxane.

In particular, when silsesquioxane in which R ² is a methyl group, an ethyl group, a phenyl group, or a biphenyl group and a is 1 is selected as the hydrolysis condensate, the crack resistance when a thick film is formed is significantly improved. ..

The weight average molecular weight of the hydrolyzed condensate of at least one hydrolyzable silane represented by the formula (1) is, for example, 1,000 to 100,000. These molecular weights are average molecular weights obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter abbreviated as GPC) analysis.

Examples of the hydrolysis catalyst for synthesizing the hydrolysis condensate include organic acids, inorganic acids, organic bases, and inorganic bases.

Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid and galvanic acid. Acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloro Examples thereof include acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate acid and the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Examples of the organic base include pyridine, pyrrol, piperazin, pyrrolidine, piperidine, picolin, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, and diazabicyclononane. , Diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene and the like. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, organic acids and inorganic acids are preferable, and one or more catalysts may be used at the same time.

For hydrolysis of an alkoxy group (hereinafter referred to as a hydrolyzing group) bonded to a silicon atom of a hydrolyzable silane, 0.1 to 100 mol or 0.1 to 10 mol per 1 mol of these hydrolyzing groups , Or 1 to 5 mol, or 2 to 3.5 mol of water is used. Further, 0.0001 to 10 mol, preferably 0.001 to 2 mol, of a hydrolysis catalyst can be used per mol of the hydrolysis group.

The reaction temperature for hydrolyzing and condensing hydrolyzable silane is usually in the range of 23 ° C. (room temperature) or higher and the reflux temperature of the organic solvent used for hydrolysis at normal pressure or lower.

The hydrolyzable silane may be completely hydrolyzed, i.e. all hydrolyzing groups may be converted to silanol groups, or partially hydrolyzed, i.e. leaving unreacted hydrolyzing groups. Further, an uncondensed hydrolyzate may remain after the hydrolysis and condensation reactions.

The method for obtaining a hydrolyzed condensate of hydrolyzable silane is not particularly limited, and examples thereof include a method of heating a mixture of a hydrolyzable silane compound, an organic solvent, water, and a catalyst for hydrolysis.
Specifically, a method in which oxalic acid (a catalyst for hydrolysis) and water are added to alcohol (organic solvent) in advance to prepare a solution of oxalic acid, and then the solution and a hydrolyzable silane compound are mixed and heated. is there. At that time, the amount of oxalic acid is generally 0.2 to 2 mol with respect to 1 mol of the total hydrolyzing group (alkoxy group or the like) contained in the hydrolyzable silane compound. The heating in this method can be performed at a liquid temperature of 50 to 180 ° C., preferably for 10 minutes to 12 hours under reflux in a closed container so that evaporation, volatilization, etc. of the liquid do not occur.
Further, in the procedure for producing a hydrolyzed condensate of hydrolyzable silane, the organic solvent, water and water are added even in the order of adding a mixture of an organic solvent, water and a hydrolyzing catalyst to the hydrolyzable silane compound and reacting them. The order may be such that the hydrolyzable silane compound is added to the mixture of the decomposition solvents and reacted.
The reaction temperature at the time of synthesizing the hydrolyzed condensate of hydrolyzable silane may be any reaction temperature of 0 to 50 ° C. for the purpose of stably synthesizing a uniform polymer, and the reaction time is 24 to 2000 hours. be able to.

The above-mentioned hydrolysis catalyst can be selected for the purpose of controlling the amount of silanol groups in the hydrolyzed condensate of the obtained hydrolyzable silane. Generally, when an acid is selected, a large amount of silanol groups remain, and a base is selected. Then, the silanol groups are reduced. A large amount of silanol groups has the effect of increasing the viscosity of the film-forming composition, and may be appropriately selected in a region where the storage stability of the film-forming composition can be maintained.

Examples of the organic solvent used for hydrolysis include toluene, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, diacetone alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, γ-butyrolactone, n-propyl acetate, ethyl lactate , N-Methyl-2-pyrrolidone and the like. These solvents can be used alone or in combination of two or more.
Among them, as the organic solvent, alcohol is generally produced by a hydrolysis reaction, so it is preferable to use an organic solvent having good compatibility with alcohols and alcohols. Specific examples of such organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol. Preferable examples thereof include monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, n-propyl acetate, ethyl lactate and cyclohexanone.

As described above, the hydrolyzed condensate (polysiloxane) of the component (A) is obtained by hydrolyzing the hydrolyzable silane in an organic solvent and subjecting the hydrolyzate to a condensation reaction, and the condensate is organic. It is obtained in the form of a polysiloxane varnish dissolved in a solvent.

The obtained polysiloxane varnish may be solvent-substituted. Specifically, when ethanol is selected as the organic solvent during the hydrolysis and condensation reactions (hereinafter referred to as the solvent during synthesis), a substitution solvent is added after the polysiloxane is obtained in ethanol, and an evaporator or the like is used. The solvent can be replaced with a replacement solvent by co-boiling and distilling off ethanol. At the time of solvent substitution, since the solvent during synthesis is azeotropically distilled off, it is preferable that the boiling point is lower than that of the solvent for substitution. For example, the solvent for synthesis includes methanol, ethanol, isopropanol and the like, and the solvent for substitution includes propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone and the like.

Further, the obtained polysiloxane varnish may have a solid content concentration of 100% by distilling off an organic solvent as long as its storage stability is not poor.

The organic solvent used for diluting the polysiloxane varnish or the like may be the same as or different from the organic solvent used for the hydrolysis reaction of the hydrolyzable silane. The dilution solvent is not particularly limited, and either one type or two or more types can be arbitrarily selected and used.

Specific examples of such an organic solvent for dilution include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl Ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy- 2-Butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyllactone, acetone , Methyl ethyl ketone, Methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert -Butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethyl Hexanol, isopropyl ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, N- Cyclohexyl-2-pyrrolidinone and the like can be mentioned.

Of these, more preferably, methanol, ethanol, isopropanol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, and butyl. Examples thereof include carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, methyl acetate, ethyl acetate and ethyl lactate.

<Ingredient (B)>
The inorganic fine particles of the component (B) contained in the film-forming composition of the present invention have metal oxide colloidal particles (B1) having a primary particle diameter of 2 to 60 nm as a core, and the surface thereof is a primary of 1 to 4 nm. A polyoxyethylene group as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating material (B2) composed of metal oxide colloidal particles having a particle size. , A type having one or more poly (oxyalkylene) groups selected from polyoxypropylene groups or polyoxybutylene groups, and one type selected from alkylene groups or vinylene groups having 1 to 18 carbon atoms as hydrophobic groups. It is an inorganic fine particle to which an amphoteric organic silicon compound having the above groups is bonded.

In the present invention, the primary particle size of colloidal particles can be measured by observation with a transmission electron microscope.

The metal oxide colloidal particles (B1) can be produced by a known method, for example, an ion exchange method, a gelatinization method, a hydrolysis method, or a reaction method. Examples of the ion exchange method include a method of treating an acidic salt of a metal with a hydrogen type ion exchange resin and a method of treating a basic salt of a metal with a hydroxyl group type anion exchange resin. As an example of the defibration method, a method of neutralizing an acidic salt of a metal with a base or washing a gel obtained by neutralizing a basic salt of a metal with an acid and then deflating with an acid or a base. Can be mentioned. Examples of the hydrolysis method include a method of hydrolyzing a metal alkoxide, or a method of hydrolyzing a basic salt of a metal under heating and then removing an unnecessary acid. An example of a reaction method is a method of reacting a metal powder with an acid.

The metal oxide colloidal particles (B1) are at least one selected from the group consisting of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. It is an oxide of a kind of metal. The colloidal particles of this metal oxide are metal oxides having a valence of 2 to 6, and the forms of the metal oxides are, for example, TiO ₂ , Fe ₂ O ₃ , CuO, ZnO, Y ₂ O ₃ , ZrO _2. , Nb ₂ O ₅ , MoO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , PbO, Bi ₂ O _{3, and the} like can be exemplified. And these metal oxides can be used alone or in combination. Examples of the combination include a method of mixing several kinds of the metal oxides, a method of compounding the metal oxides, and a method of solidifying the metal oxides at the atomic level.

For example, the SnO _2- WO ₃ composite colloidal particles in which the SnO ₂ particles and the WO ₃ particles form a chemical bond at the interface and are composited, and the SnO ₂ particles and the ZrO ₂ particles are chemically bonded at the interface. include a _SnO 2 -ZrO ₂ composite colloidal particles complexed occurs, _TiO 2 -ZrO ₂ -SnO ₂ composite colloidal particles, TiO _2, ZrO ₂ and SnO ₂ are obtained by forming a solid solution at the atomic level Be done. The metal oxide colloid particles (B1) may also be used as a compound with a combination of metal components, include, for example, _{ZnSb 2 O 6, InSbO 4,} ZnSnO 3.

In the present invention, the metal oxide colloidal particles (B1) are used as nuclei, and the surface thereof is coated with a coating material (B2) composed of metal oxide colloidal particles having a primary particle diameter of 1 to 4 nm. (B3) is obtained, and one or more poly (oxyalkylene) groups selected from polyoxyethylene groups, polyoxypropylene groups, and polyoxybutylene groups are provided on the surface thereof as hydrophilic groups, and as hydrophobic groups. Inorganic fine particles of the component (B) can be obtained by bonding an organic silicon compound having one or more groups selected from an alkylene group having 1 to 18 carbon atoms or a vinylene group.

The metal oxide used in the coating (B2) is a colloidal particle of an oxide of at least one metal selected from the group consisting of Si, Al, Sn, Zr, Mo, Sb and W. Examples of the metal oxide form of the coating (B2) include SiO ₂ , Al ₂ O ₃ , SnO ₂ , ZrO ₂ , MoO ₃ , Sb ₂ O ₅ , WO _{3, and the} like. And these metal oxides can be used alone or in combination. Examples of the combination include a method of mixing several kinds of the metal oxide, a method of compounding the metal oxide, and a method of solidifying the metal oxide at the atomic level.

For example, the SnO _2- WO ₃ composite colloidal particles in which the SnO ₂ particles and the WO ₃ particles form a chemical bond at the interface and are composited, and the SnO ₂ particles and the SiO ₂ particles are chemically bonded at the interface. _SnO 2 -SiO ₂ composite colloidal particles complexed occurs a, _SnO 2 _-WO 3 -SiO where the SnO ₂ particles and WO ₃ particles and SiO ₂ particles are complexed occurs a chemical bonding at the interface ₂ composite colloidal particles, SnO ₂ particles and MoO ₃ particles and _SnO 2 -MoO and SiO ₂ particles are complexed occurs a chemical bonding at the interface ₃ -SiO ₂ composite colloidal particles, and _Sb 2 _{O 5} particles and SiO ₂ particles chemically bonded to occur which are complexes of _{Sb 2 O} 5 -SiO 2 composite colloidal particles, and the like at the interface.

The coating material (B2) can be produced by a known method, for example, an ion exchange method or an oxidation method. Examples of the ion exchange method include a method of treating the acid salt of the metal with a hydrogen type ion exchange resin. Examples of the oxidation method include a method of reacting the above metal or metal oxide powder with hydrogen peroxide.

Examples of the method for producing the modified metal oxide colloidal particles (B3) include the following first and second methods.

As the first method, the aqueous sol containing the metal oxide colloidal particles (B1) as the nucleus and the aqueous sol containing the coating material (B2) were converted into the respective metal oxides (B2) / (. This is a method in which the mixed sol is heated after mixing so that the mass ratio of B1) is 0.05 to 0.5.
For example, an aqueous sol containing metal oxide colloidal particles (B1) and an Sb ₂ O ₅ −SiO ₂ composite colloid having a mass ratio of Sb ₂ O ₅ / SiO ₂ as a coating (B2) of 0.1 to _5. The aqueous sol containing the particles was mixed so that the mass ratio of (B2) / (B1) converted to each metal oxide was 0.05 to 0.5, and the mixed sol was mixed at 70 to 350 ° C. By heating with, a modified metal oxide sol composed of particles (B3) having the metal oxide colloidal particles (B1) as nuclei and the surface of which is coated with Sb ₂ O _5- SiO ₂ composite colloidal particles (B2) is obtained. Be done.

In addition, as a second method, an aqueous sol containing metal oxide colloidal particles (B1) as a nucleus and a water-soluble tin oxide alkali salt and a water-soluble silicon oxide alkali salt as a coating (B2) are used. After mixing so that the mass ratio of SnO ₂ / SiO ₂ converted to each metal oxide was 0.1 to 5, cation exchange was performed to remove alkali metal ions, and the obtained composite colloidal particles were obtained. This is a method of mixing and heating the aqueous sol of the above. As the aqueous solution of the water-soluble alkaline salt used in this second method, an aqueous solution of a sodium salt can be preferably used.
For example, a SnO _2- SiO ₂ composite obtained by mixing an aqueous sol containing metal oxide colloidal particles (B1) and an aqueous solution of sodium nitrate and sodium silicate as a coating (B2) and then exchanging cations. and an aqueous sol of colloidal particles, and mixed such that 0.05 to 0.5 at a mass ratio of in terms of each of the metal oxide _{(SnO 2 -SiO 2) / (} B2), 70 the aqueous sol by heating at to 350 ° C., the metal oxide colloid particles (B1) as nuclei, coating (B2) coated with modified metal oxide colloidal particles comprising the surface from _SnO 2 -SiO ₂ composite colloidal particles ( The aqueous sol of B3) is obtained.

The mixing of the colloidal particles (B1) of the metal oxide and the coating (B2) can be performed at a temperature of 1 to 100 ° C., preferably room temperature to 60 ° C. The heating after mixing is preferably performed at 70 to 350 ° C.

The sol of the modified metal oxide colloidal particles (B3) can contain any other component as long as the object of the present invention is achieved. In particular, when oxycarboxylic acids are contained in a proportion of about 30% by mass or less with respect to the total amount of all metal oxides, a colloid having further improved performance such as dispersibility can be obtained. Examples of the oxycarboxylic acid used include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, glycol and the like.

Further, the sol of the modified metal oxide colloidal particles (B3) can contain an alkaline component, for example, hydroxides of alkali metals such as Li, Na, K, Rb and Cs, ammonia, ethylamine and isopropylamine. , N-propylamine, n-butylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, triamylamine, tri- 1-3-class alkylamines such as n-hexylamine, tri-n-octylamine, dimethylpropylamine, dimethylbutylamine, and dimethylhexylamine, aralkylamines such as benzylamine and dimethylbenzylamine, and alicyclic amines such as piperidine, Examples thereof include alkanolamines such as monoethanolamine and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. These alkaline components can be contained alone or in admixture of two or more. The alkaline component can be contained in a proportion of about 30% by mass or less with respect to the total metal oxide of the modified metal oxide colloidal particles (B3). It can also be used in combination with the above-mentioned oxycarboxylic acids.

When the sol of the modified metal oxide colloidal particles (B3) is an aqueous sol, an organic solvent sol can be obtained by substituting the aqueous medium of the aqueous sol with a hydrophilic organic solvent. This substitution can be performed by a usual method such as a distillation method or an ultrafiltration method. Examples of this hydrophilic organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ethers such as propylene glycol monomethyl ether, linear amides such as dimethylformamide, N, N'-dimethylacetamide, and N. Examples thereof include cyclic amides such as -methyl-2-pyrrolidone, and glycols such as ethyl cellosolve and ethylene glycol.

The inorganic fine particles as the component (B) of the present invention are selected from a polyoxyethylene group, a polyoxypropylene group or a polyoxybutylene group as a hydrophilic group on the surface of the modified metal oxide colloidal particles (B3) 1 An amphipathic organic silicon compound having a poly (oxyalkylene) group of one or more species and having one or more groups selected from an alkylene group having 1 to 18 carbon atoms or a vinylene group as a hydrophobic group was bonded. It is a thing.

In one molecule of the amphipathic organosilicon compound, the number of added moles of the polyoxyethylene group, polyoxypropylene group or polyoxybutylene group which is the hydrophilic group is preferably 3 to 40.

Specific examples of the amphoteric organic silicon compound used in the present invention include methoxytriethyleneoxypropyltrimethoxysilane, methoxytriethyleneoxyoctyltrimethoxysilane, methoxytriethyleneoxypropyltriethoxysilane, and methoxytriethyleneoxypropyl. Tripropoxysilane, methoxytriethyleneoxypropyltriacetoxysilane, methoxytripropyleneoxypropyltrimethoxysilane, methoxytripropyleneoxyoctyltrimethoxysilane, methoxytripropyleneoxypropyltriethoxysilane, methoxytripropyleneoxypropyltripropoxysilane, methoxy Tripropyleneoxypropyltriacetoxysilane, methoxytributyleneoxypropyltrimethoxysilane, methoxytributyleneoxyoctyltrimethoxysilane, methoxytributyleneoxypropyltriethoxysilane, methoxytributyleneoxypropyltripropoxysilane, methoxytributyleneoxypropyltri Acetoxysilane, methoxytriethyleneoxypropyldimethoxymethylsilane, methoxytripropyleneoxydimethoxymethylsilane, methoxytributyleneoxydimethoxymethylsilane, methoxytriethyleneoxypropyldiethoxymethylsilane, methoxytripropyleneoxydiethoxymethylsilane, methoxytributylene Oxydiethoxymethylsilane, methoxytriethyleneoxypropyldimethylmethoxysilane, methoxytripropyleneoxypropyldimethylmethoxysilane, methoxytributyleneoxypropyldimethylmethoxysilane, methoxytriethyleneoxypropyldimethylethoxysilane, methoxytripropyleneoxypropyldimethylethoxysilane , Methoxytributylene oxypropyldimethylethoxysilane, bis- (methoxytriethyleneoxypropyl) dimethoxysilane, bis- (methoxytripropyleneoxypropyl) dimethoxysilane, bis- (methoxytributyleneoxypropyl) dimethoxysilane, [methoxy (poly) (Ethethyleneoxy) n) propyl] trimethoxysilane, [methoxy (poly (ethyleneoxy) n) propyl] triethoxysilane, [methoxy (poly (ethyleneoxy) n) propyl] tripropoxysilane, [methoxy (poly (ethyleneoxy) n) propyl] tripropoxysilane Oxy) n) Propyl] triacetoxysilane, [methoxy (poly (propyleneoxy) n) propyl] trimethoxysilane, [methoxy (poly (propyleneoxy) n) propyl] triethoxysilane, [methoxy (poly (propyleneoxy) n) propyl] Tripropoxysilane, "methoxy (poly (propyleneoxy) n) propyl" triacetoxysilane, [methoxy (poly (butyleneoxy) n) propyl] trimethoxysilane, [methoxy (poly (butyleneoxy) n) propyl] tripropoxy Silane, [methoxy (poly (butyleneoxy) n) propyl] triacetoxysilane, [methoxy (poly (ethyleneoxy) n) propyl] dimethoxymethylsilane, [methoxy (poly (ethyleneoxy) n) propyl] diethoxymethylsilane , [Methoxy (poly (ethyleneoxy) n) propyl] dipropoxymethylsilane, [methoxy (poly (ethyleneoxy) n) propyl] diacetoxymethylsilane, [methoxy (poly (propyleneoxy) n) propyl] dimethoxymethylsilane , [Methoxy (poly (propyleneoxy) n) propyl] diethoxymethylsilane, [methoxy (poly (propyleneoxy) n) propyl] dipropoxymethylsilane, [methoxy (poly (propyleneoxy) n) propyl] diacetoxymethyl Silane, [methoxy (poly (butyleneoxy) n) propyl] dimethoxymethylsilane, [methoxy (poly (butyleneoxy) n) propyl] diethoxymethylsilane, [methoxy (poly (butyleneoxy) n) propyl] dipropoxymethyl Examples thereof include silane, [methoxy (poly (butyleneoxy) n) propyl] diacetoxymethylsilane and the like (n = 3 to 40).

The amount of the amphoteric organic silicon compound bonded to the surface of the modified metal oxide colloidal particles (B3) is 0.1 to 30 mass by mass with respect to the total metal oxide of the modified metal oxide colloidal particles (B3). % Is preferable, and more preferably 1 to 15% by mass.

The inorganic fine particles which are the component (B) of the present invention are prepared by adding a predetermined amount of the amphoteric organic silicon compound to the aqueous sol or hydrophilic organic solvent sol of the modified metal oxide colloidal particles (B3), and using dilute hydrochloric acid or the like. It can be obtained by hydrolyzing the organic silicon compound with a catalyst and binding it to the surface of the modified metal oxide colloidal particles (B3).

The film-forming composition of the present invention may contain any other component as long as the object of the present invention is achieved. In particular, when phosphoric acid, a phosphoric acid-based derivative, a phosphoric acid-based surfactant, and an oxycarboxylic acid are contained in a ratio of about 30% by mass or less with respect to the total metal oxide of the modified metal oxide colloidal particles (B3). , A film-forming composition in which the dispersibility of the inorganic fine particles contained in the composition is further improved can be obtained. Examples of the phosphoric acid derivative used include phenylphosphonic acid and a metal salt thereof. Examples of the phosphoric acid-based surfactant include Disperbyk (Big Chemie), Phosphanol (registered trademark) (Toho Chemical Industry Co., Ltd.), Nikkor (registered trademark) (Nikko Chemicals Co., Ltd.) and the like. Examples of the oxycarboxylic acid include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, glycol and the like.

<Method for manufacturing composition for film formation>
The present invention also comprises the component (A): the following formula (1).

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
Hydrolyzed condensate of at least one hydrophilic silane represented by and component (B): Metal oxide colloidal particles (B1) having a primary particle diameter of 2 to 60 nm are used as nuclei, and the surface thereof is 1 to 4 nm. Polyoxy as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating (B2) composed of metal oxide colloidal particles having a primary particle size. It has one or more poly (oxyalkylene) groups selected from an ethylene group, a polyoxypropylene group or a polyoxybutylene group, and is selected from an alkylene group having 1 to 18 carbon atoms or a vinylene group as a hydrophobic group. The subject is a method for producing a film-forming composition, which comprises a step of mixing with inorganic fine particles to which an amphoteric organic silicon compound having one or more groups is bonded.

The method for mixing the component (A) and the component (B) is as follows.
(A) A method of mixing the component (A) in a solid state with a dispersion of the component (B).
(B) A method of mixing the component (A) with the dispersion of the component (B) in the state of a solution in which the component (A) is dissolved and dispersed in an organic solvent or the like.
(C) A method of simultaneously adding and mixing the component (A) in a solid state in the step of dispersing the component (B) in a dispersion medium can be mentioned.
Among these, since the operation is easy, it is preferable to mix by the method (b).

The solvent used in the above-mentioned production method may be the same as the solvent used for the component (A) and the solvent used for the component (B) as long as the stability of the film-forming composition of the present invention is not impaired. , But when the solvents are different, it is preferable that the polarities of the two solvents are close to each other.

Specific examples of the solvent used in the present invention include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, and propylene glycol mono. Ethylene ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether , Dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol , 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ -Butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol , Isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol , 2-Ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, dimethylsulfoxide, N-cyclohexyl -2-pyrrolidinone and the like can be mentioned, and these may be used alone or in combination of two or more.

The film-forming composition of the present invention may include a step of mixing the component (A) and the component (B) followed by a step of heating. For example, the heating conditions are 23 ° C. or higher, preferably 50 ° C. or higher, more preferably 70 ° C. or higher, 150 ° C. or lower, preferably 140 ° C. or lower, after mixing the component (A) and the component (B). It is preferably 120 ° C. or lower. The heating time is preferably 1 to 48 hours. When the film-forming composition of the present invention is obtained by heating, a film having a uniform film quality may be obtained.

The content of the component (B) in the film-forming composition of the present invention may be as long as the dispersibility of the obtained film-forming composition is not impaired, and the desired refractive index and transmittance of the film to be produced are not impaired. It can be appropriately controlled according to the rate and heat resistance.

For example, when the hydrolyzable condensate of the hydrolyzable silane of the component (A) is 100 parts by mass in terms of solid content, the inorganic fine particles of the component (B) are in the range of 0.1 to 1,500 parts by mass. It can be added, preferably 100 to 1,000 parts by mass, and more preferably 300 to 700 parts by mass in order to retain the film quality and obtain a stable refractive index. Here, the solid content of the hydrolyzed condensate of hydrolyzable silane is the solid content after firing at 140 ° C.

The film-forming composition of the present invention may contain other components such as a surfactant, a cross-linking agent, a leveling agent, an anti-sedimenting agent, and an emulsifier as long as the effects of the present invention are not impaired.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol. Polyoxyethylene alkylaryl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Such as sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as sorbitan fatty acid esters, trade name Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd. (formerly Gemco Co., Ltd.), trade name Megafuck (registered trademark) ) F171, F173, R-08, R-30 (manufactured by DIC Co., Ltd.), Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name Asahi Guard (registered trademark) AG710, surflon (registered) Fluorophilic surfactants such as S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Organosiloxane polymer KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by BIC Chemie Japan Co., Ltd.) and the like can be mentioned.

These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 3 parts by mass, still more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (A).

The cross-linking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the component (A). Such compounds include melamine compounds having cross-linking substituents such as methylol group and methoxymethyl group, substituted urea compounds, compounds containing cross-linking substituents such as epoxy group and oxetane group, and blocked isocyanate. Examples thereof include compounds having an acid anhydride, compounds having a (meth) acrylic group, and phenoplast compounds, but from the viewpoint of heat resistance and storage stability, epoxy groups, blocked isocyanate groups, and (meth) acrylic groups A compound containing is preferable.

These cross-linking agents may be used alone or in combination of two or more. The amount of the cross-linking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the component (A), but the upper limit thereof is preferably 2 parts by mass, more preferably 5 in consideration of having a high refractive index. It is a mass part. By using a cross-linking agent, the cross-linking agent may react with the reactive terminal silanol group of the component (A) to exhibit effects such as improvement of film density, heat resistance, and heat relaxation ability. is there.

The above-mentioned other components can be added at any step when preparing the film-forming composition of the present invention.

The film-forming composition of the present invention can be applied to a substrate and then fired, if necessary, to form a desired film. The coating is also the subject of the present invention.

The coating method of the film-forming composition of the present invention is arbitrary, for example, spin coating method, dip method, flow coating method, inkjet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method. , Transfer printing method, brush coating, blade coating method, air knife coating method and the like can be adopted.

Further, as the base material, silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics. Examples thereof include a base material made of the above, and a flexible base material having flexibility can also be used.

The film-forming composition of the present invention can be filtered before use, and is not particularly limited in the effective filtration area and material of the filter medium, and may be filtered according to the target product.

After the film-forming composition is applied to the substrate, it can be fired for the purpose of evaporating the solvent. The firing temperature is not particularly limited, and the firing temperature can be, for example, 40 to 400 ° C. In the firing, the distribution of the film thickness is not biased, high uniformity is exhibited, and the reaction of the cross-linking agent or the like is allowed to proceed on the substrate, even if the temperature is changed in two or more steps. Good.

The firing method is not particularly limited, and for example, the solvent may be evaporated in the atmosphere, an inert gas such as nitrogen, or in a vacuum or the like using a hot plate or an oven.

For the firing temperature and firing time, conditions suitable for the manufacturing process of the target electronic device may be selected, and firing conditions may be selected so that the physical property values of the obtained film match the required characteristics of the electronic device.

The film (coating) made of the composition of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage. Therefore, a liquid crystal display and an organic electro It can be suitably used as a member for manufacturing electronic devices such as liquid crystal displays (EL) displays, optical semiconductor (LED) elements, solid-state imaging devices, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs). As described above, an electronic device including a base material and a film formed of the composition of the present invention formed on the base material, an optical member, and a solid-state image sensor having a complementary metal oxide semiconductor having the film. Alternatively, a charge-binding element, an implant material for a solid-state image sensor, a flattening material, or a microlens material is also an object of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measuring devices used in the examples are as follows.
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: tetrahydrofuran (hereinafter, THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [ultraviolet visible spectrophotometer]
Equipment: SHIMADZU UV-3600 manufactured by Shimadzu Corporation
[Ellipsometer]
Equipment: J.A. Woolam Japan Co., Ltd. Multi-incident angle spectroscopic ellipsometer VASE
[viscosity]
Equipment: E-type viscometer manufactured by Toki Sangyo Co., Ltd. (20 ° C)
[electronic microscope]
Equipment: Hitachi High-Technologies Corporation S-4800

[Synthesis Example 1] Synthesis of Polysiloxane [S1] Using Tetraethoxysilane as a Raw Material 29.17 g (0.14 mol) of tetraethoxysilane and 116.66 g of propylene glycol monomethyl ether (hereinafter abbreviated as PGME) are 300 ml. To the mixed solution, 10.09 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 100 ° C. and reacted under heating under reflux for 240 minutes. Then, the reaction solution is cooled to room temperature, 116.66 g of PGME is added to the reaction solution, ethanol, water and hydrochloric acid, which are reaction by-products, are distilled off under reduced pressure, and the mixture is concentrated to form a PGME solution of a hydrolyzed condensate (polymer). Got Then, PGME was added and adjusted so as to be 52% by mass in terms of solid residue at 140 ° C. The obtained polymer is a polysiloxane (abbreviated as S1) varnish made from tetraethoxysilane. The weight average molecular weight of the obtained S1 by GPC was Mw1823 in terms of polystyrene.

[Synthesis Example 2] Synthesis of Polysiloxane [S2] Using Triethoxyphenylsilane as a Raw Material The starting material of Synthesis Example 1 was changed from tetraethoxysilane to triethoxyphenylsilane, and 3.0 equivalents of pure silane monomer was used. The synthesis was carried out in the same manner except that water was used to obtain polysiloxane (abbreviated as S2). The weight average molecular weight was Mw1251.

[Synthesis Example 3] Synthesis of polysiloxane [S3] using 4-biphenyltrimethoxysilane as a raw material Same as Synthesis Example 1 except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to 4-biphenyltrimethoxysilane. To obtain polysiloxane (abbreviated as S3). The weight average molecular weight was Mw1546.

[Synthesis Example 4] Synthesis of Polysiloxane [S4] Using Methyltriethoxysilane as a Raw Material Synthesis was carried out in the same manner as in Synthesis Example 1 except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to methyltriethoxysilane. Polysiloxane (abbreviated as S4) was obtained. The weight average molecular weight was Mw2979.

[Synthesis Example 5] Synthesis of Polysiloxane [S5] Using Ethyltriethoxysilane as a Raw Material Synthesis was carried out in the same manner as in Synthesis Example 1 except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to ethyltriethoxysilane. Polysiloxane (abbreviated as S5) was obtained. The weight average molecular weight was Mw2744.

[Synthesis Example 6] Synthesis of Polysiloxane [S6] Using Propyltriethoxysilane as a Raw Material Synthesis was carried out in the same manner as in Synthesis Example 1 except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to propyltriethoxysilane. Polysiloxane (abbreviated as S6) was obtained. The weight average molecular weight was Mw2154.

[Synthesis Example 7] Synthesis of polysiloxane [S7] using isobutyltriethoxysilane as a raw material Synthesis was carried out in the same manner as in Synthesis Example 1 except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to isobutyltriethoxysilane. Polysiloxane (abbreviated as S7) was obtained. The weight average molecular weight was Mw1560.

[Synthesis Example 8] Synthesis of polysiloxane [S8] using n-octyltriethoxysilane as a raw material Same as Synthesis Example 1 except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to n-octyltriethoxysilane. To obtain polysiloxane (abbreviated as S8). The weight average molecular weight was Mw1371.

[Synthesis Example 9] Synthesis of polysiloxane [S9] using 9-phenanthryltrimethoxysilane as a raw material Synthesis except that the starting material of Synthesis Example 2 was changed from triethoxyphenylsilane to 9-phenanthriltrimethoxysilane. Synthesis was carried out in the same manner as in Example 1 to obtain polysiloxane (abbreviated as S9). The weight average molecular weight was Mw1521.

[Synthesis Example 10] Synthesis of polysiloxane [S10] using dimethoxydimethylsilane as a raw material The starting material of Synthesis Example 1 was changed from tetraethoxysilane to dimethoxydimethylsilane, and 2.0 equivalents of pure water was added to the silane monomer. A polysiloxane (abbreviated as S10) was obtained by synthesizing in the same manner as in Synthesis Example 1 except that it was used. The weight average molecular weight was Mw2516.

[Synthesis Example 11] Synthesis of polymethyl methacrylate [R1] 92 g of propylene glycol monomethyl ether acetate (PGMEA) was charged into a 200 mL reaction flask, and then 20 g of methyl methacrylate and 3 g of azobisisobutyronitrile were charged. , Nitrogen was poured for 5 minutes with stirring to perform nitrogen substitution. After visually confirming that the solute in the solution was completely dissolved, the reaction was carried out at an internal temperature of 100 ° C. for 12 hours. The reaction was then poured into 575 g of methanol to precipitate the polymer. The obtained solid was separated by vacuum filtration, and the solid was dried in a vacuum dryer at 50 ° C. for 12 hours. The Mw of polymethylmethacrylate [R1] obtained by drying by GPC was 3500. PGME was added and dissolved so that R1 was 52% by mass in terms of solid residue at 140 ° C. to obtain a polymer solution.

[Synthesis Example 12] Synthesis of polystyrene [R2] 92 g of propylene glycol monomethyl ether acetate (PGMEA) is charged in a 200 mL reaction flask, then 20 g of styrene and 3 g of azobisisobutyronitrile are charged, and the mixture is stirred. Nitrogen was poured for a minute to perform nitrogen substitution. After visually confirming that the solute in the solution was completely dissolved, the reaction was carried out at an internal temperature of 100 ° C. for 12 hours. The reaction was then poured into 575 g of methanol to precipitate the polymer. The obtained polymer was separated by vacuum filtration and dried in a vacuum dryer at 50 ° C. for 12 hours. The GPC Mw of the polystyrene [R2] obtained by drying was 3810. R2 was dissolved by adding PGME so as to be 52% by mass in terms of solid residue at 140 ° C. to obtain a polymer solution.

[Synthesis Example 13] Synthesis of dispersion liquid of component (B) A dispersion sol of titanium oxide-containing nuclear particles (abbreviated as T1) of component (B) was prepared as follows.
<Preparation of nuclear particles (B1)>
Put 126.2 g of pure water in a 1 liter container, 17.8 g of metasuccinic acid (containing 15 g in terms of SnO ₂ ), 284 g of titanium tetraisopropoxide (containing 80 g in terms of TiO ₂ ), 84 g of oxalic acid dihydrate (containing 80 g in terms of TiO ₂ ). 438 g of a 35 mass% tetraethylammonium hydroxide aqueous solution (70 g in terms of oxalic acid) was added under stirring. The obtained mixed solution had a molar ratio of oxalic acid / titanium atom of 0.78 and a molar ratio of tetraethylammonium hydroxide / titanium atom of 1.04. 950 g of the mixed solution was held at 80 ° C. for 2 hours, further reduced to 580 Torr and held for 2 hours to prepare a titanium mixed solution. The pH of the titanium mixed solution after preparation was 4.7, and the TiO ₂ concentration was 8.4% by mass. 950 g of the titanium mixture solution and 950 g of pure water were put into a 3 liter glass-lined autoclave container, and hydrothermal treatment was performed at 140 ° C. for 5 hours. After cooling to room temperature, the solution after hydrothermal treatment taken out was an aqueous dispersion sol of pale milky white titanium oxide colloidal particles. The obtained sol had a pH of 3.9, a TiO ₂ concentration of 4.2% by mass, tetraethylammonium hydroxide of 4.0% by mass, oxalic acid of 1.8% by mass, a dynamic light scattering method particle diameter of 16 nm, and a transmission electron microscope. In the observation, elliptical particles having a primary particle diameter of 5 to 15 nm were observed. X-ray diffraction analysis of the powder obtained by drying the obtained sol at 110 ° C. was performed, and it was confirmed that it was a rutile type crystal. The obtained titanium oxide colloidal particles were designated as titanium oxide-containing nuclear particles (B1).

<Preparation of coating (B2)>
Next, 27.9 g of an aqueous sodium silicate solution (No. 3 silicate, containing 34% by mass as SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) was diluted with 27.9 g of pure water, and then sodium silicate and 3 water were added. 8.6 g of a Japanese product (containing 55% by mass as SnO ₂ , manufactured by Showa Kako Co., Ltd.) was added and dissolved under stirring to obtain an aqueous solution of sodium silicate-sodium silicate. 64.4 g of the obtained sodium silicate aqueous solution is diluted with 411 g of pure water and passed through a column packed with a hydrogen type cation exchange resin (Amberlite (registered trademark) IR-120B, Organo Co., Ltd.). Accordingly, silicon dioxide - water dispersion sol (pH 2.7 stannate composite oxide colloidal particles, 0.83% by mass as SnO _2, containing 1.67% by mass as SiO _2, SiO 2 / SnO ₂ weight ratio of 2. 0) 570 g was obtained. Then, 2.9 g of diisopropylamine was added to the obtained aqueous dispersion sol. The obtained sol was an aqueous dispersion sol of alkaline silicon dioxide-tin acid composite oxide colloidal particles, and was a sol of colloidal particles having a pH of 8.2 and a primary particle diameter of 5 nm or less. The obtained silicon dioxide-tin acid composite oxide colloidal particles were used as a coating material (B2).

<Preparation of modified metal oxide colloidal particles (B3)>
Next, after adding 570 g of a coating material (B2) composed of silicon dioxide-silicic acid composite oxide colloidal particles to 1900 g of titanium oxide-containing nuclear particles (B1) under stirring, the mixture was held at a temperature of 95 ° C. for 3 hours to modify titanium oxide. An aqueous sol of composite colloidal particles was obtained. Then, the obtained aqueous sol of the modified titanium oxide composite colloidal particles was passed through a column packed with a hydrogen type cation exchange resin (Amberlite (registered trademark) IR-120B, Organo Co., Ltd.), and the acidic modified titanium oxide was passed. 2730 g of an aqueous sol of composite colloidal particles was obtained. The obtained sol had a pH of 2.7 and a total metal oxide concentration of 4.0% by mass. 2.2 g of diisobutylamine was added to the obtained sol. The pH of the sol at this time was 4.5. Next, the obtained sol was put into an evaporator with a eggplant-shaped flask to concentrate, and water was distilled off at 600 Torr while adding methanol to 533 g of a methanol sol of modified titanium oxide colloidal particles (B3) to which diisobutylamine was bound. Got The obtained methanol sol had a specific gravity of 0.949, a viscosity of 1.2 mPa · s, a pH of 4.8 (diluted with water having the same mass as the sol), a total metal oxide concentration of 20.5 mass%, and a water content of 3.1%. there were.

<Preparation of inorganic fine particles (B) to which an organosilicon compound is bound>
5.5 g of a polyether-modified silane (3- [methoxy (polyethyleneoxy) npropyl] trimethoxysilane (n = 5 to 15); manufactured by Shinetsu Silicone: trade name X-12-641) was added to 533 g of the obtained methanol sol. The mixture was added and subjected to distillation heating for 5 hours to bond the polyether-modified silane to the surface of the modified titanium oxide colloidal particles. Then, by distilling off methanol while adding propylene glycol monomethyl ether at 80 Torr using an evaporator, methanol was replaced with propylene glycol monomethyl ether as a solvent, and modified titanium oxide colloidal particles in which polyether-modified silane was bonded to the surface were obtained. 270 g of propylene glycol monomethyl ether dispersion sol was obtained. The obtained sol has a specific gravity of 1.353, a viscosity of 7.0 mPa · s, a total metal oxide concentration of 40.3 mass%, a primary particle diameter of 5 to 10 nm as observed by a transmission electron microscope, and a dynamic light scattering particle diameter. Was 9 nm. The content of the polyether-modified silane bonded to the surface of the modified titanium oxide colloidal particles was 4.0% by mass with respect to the modified titanium oxide colloidal particles. Then, it was concentrated using an evaporator so as to have a solid residue equivalent of 52% by mass at 140 ° C. to obtain a metal oxide sol (T1) as a component (B).

[Synthesis Example 14] Synthesis of metal oxide sol not contained in component (B) A dispersed sol of titanium oxide-containing nuclear particles (abbreviated as T2) was prepared as follows.
<Preparation of metal oxide colloidal particles>
Put 126.2 g of pure water in a 1 liter container, 17.8 g of metasuccinic acid (containing 15 g in terms of SnO ₂ ), 284 g of titanium tetraisopropoxide (containing 80 g in terms of TiO ₂ ), 84 g of oxalic acid dihydrate (containing 80 g in terms of TiO ₂ ). 438 g of a 35 mass% tetraethylammonium hydroxide aqueous solution (70 g in terms of oxalic acid) was added under stirring. The obtained mixed solution had a molar ratio of oxalic acid / titanium atom of 0.78 and a molar ratio of tetraethylammonium hydroxide / titanium atom of 1.04. 950 g of the mixed solution was held at 80 ° C. for 2 hours, further reduced to 580 Torr and held for 2 hours to prepare a titanium mixed solution. The pH of the titanium mixed solution after preparation was 4.7, and the TiO ₂ concentration was 8.4% by mass. 950 g of the titanium mixture solution and 950 g of pure water were put into a 3 liter glass-lined autoclave container, and hydrothermal treatment was performed at 140 ° C. for 5 hours. After cooling to room temperature, the solution after hydrothermal treatment taken out was an aqueous sol of pale milky white titanium oxide colloidal particles. The obtained sol had a pH of 3.9, a TiO ₂ concentration of 4.2% by mass, tetraethylammonium hydroxide of 4.0% by mass, oxalic acid of 1.8% by mass, a dynamic light scattering method particle diameter of 16 nm, and a transmission electron microscope. In the observation, elliptical particles having a primary particle diameter of 5 to 15 nm were observed. X-ray diffraction analysis of the powder obtained by drying the obtained sol at 110 ° C. was performed, and it was confirmed that it was a rutile type crystal.

<Preparation of metal oxide colloidal particles to be a coating>
Next, 27.9 g of an aqueous sodium silicate solution (No. 3 silicate, containing 34% by mass as SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) was diluted with 27.9 g of pure water, and then sodium silicate trihydrate. 8.6 g (containing 55% by mass as SnO ₂ , manufactured by Showa Kako Co., Ltd.) was added and dissolved under stirring to obtain an aqueous solution of sodium silicate-sodium silicate. Silicon dioxide-silicon dioxide-is obtained by diluting 64.4 g of the obtained sodium silicate aqueous solution with 411 g of pure water and passing it through a column packed with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B). aqueous sol of stannic acid composite oxide colloidal particles (pH 2.7, 0.83% by mass as SnO _2, containing 1.67% by mass as SiO _2, SiO ₂ / SnO ₂ mass ratio of 2.0) was obtained 570g .. Then, 2.9 g of diisopropylamine was added to the obtained aqueous sol. The obtained sol was an aqueous sol of alkaline silicon dioxide-tinic acid composite oxide colloidal particles, and was a colloidal particle having a pH of 8.2 and a primary particle diameter of 5 nm or less. The obtained silicon dioxide-tin acid composite oxide colloidal particles were used as a coating material.

<Preparation of modified metal oxide colloidal particles>
Next, after adding 570 g of a coating material composed of silicon dioxide-tinic acid composite oxide colloidal particles to 1900 g of an aqueous sol of titanium oxide-containing nuclear particles under stirring, the particles were kept at a temperature of 95 ° C. for 3 hours to modify the modified titanium oxide composite colloidal particles. Aqueous sol was obtained. Then, the obtained aqueous sol of the modified titanium oxide composite colloidal particles was passed through a column packed with a hydrogen type cation exchange resin (Amberlite (registered trademark) IR-120B, Organo Co., Ltd.), and the acidic modified titanium oxide was passed. 2730 g of an aqueous sol of composite colloidal particles was obtained. The obtained sol had a pH of 2.7 and a total metal oxide concentration of 4.0% by mass. 2.2 g of diisobutylamine was added to the obtained sol. The pH of the sol at this time was 4.5. Next, the obtained sol was put into an evaporator with an eggplant-shaped flask and concentrated, and water was distilled off at 600 Torr while adding methanol to obtain 364 g of a methanol-dispersed sol of modified titanium oxide colloidal particles.
The obtained methanol-dispersed sol has a specific gravity of 1.062, a viscosity of 1.8 mPa · s, a pH of 4.8 (diluted with water having the same mass as the sol), a total metal oxide concentration of 30.5 mass%, and a water content of 1.0%. Met. Then, it was concentrated using an evaporator so as to be 52% by mass in terms of solid residue at 140 ° C. to obtain a metal oxide sol (T2).

[2] Preparation of film-forming composition and film [Example 1]
(Preparation of SV1)
15.00 g of T1 obtained in Synthesis Example 13 was weighed into a 20 mL eggplant-shaped flask, then 1.5676 g of PGME was added, 3.00 g of S1 obtained in Synthesis Example 1 was added, and the mixture was mixed at room temperature to 140. A film-forming composition (SV1) having a solid content concentration of 48% by mass at the time of firing at ° C. was prepared.
(Preparation of SV1C)
10.00 g of SV1 was weighed in a 20 mL eggplant-shaped flask and heated at 80 ° C. for 1 hour using an oil bath. After heating, the mixture was allowed to cool until the internal temperature reached 23 ° C. to obtain a film-forming composition SV1C after heating.

(Viscosity measurement)
The initial viscosities of SV1 and SV1C were measured respectively, and a standing test was conducted at 23 ° C. for 30 days, and the viscosities after 30 days were measured.
(Preparation and evaluation of coating)
SV1 or SV1C is spin-coated on a silicon substrate or quartz substrate at 1000 rpm for 30 seconds using a spin coater, and then fired at 80 ° C. for 1 minute and then at 230 ° C. for 5 minutes using a hot plate to coat the film. Got
In the film obtained on the silicon substrate, the film thickness and the refractive index at a wavelength of 550 nm were measured using an ellipsometer, and in the film obtained on the quartz substrate, the transmittance was measured, and the average of 400 nm to 800 nm was measured. The transmittance was calculated.
In addition, it was tested whether whitening and cracks were visually confirmed in the film obtained on the silicon substrate. When whitening or cracks occurred, it was judged as x, and when it did not occur, it was judged as 〇.

[Example 2]
A film-forming composition (SV2) was prepared in the same manner except that S1 in Example 1 was changed to S2, and SV2 was further heated by the same method to obtain a film-forming composition SV2C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 3]
A film-forming composition (SV3) was prepared in the same manner except that S1 in Example 1 was changed to S3, and SV3 was further heated by the same method to obtain a film-forming composition SV3C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 4]
A film-forming composition (SV4) was prepared in the same manner except that S1 in Example 1 was changed to S4, and SV4 was further heated by the same method to obtain a film-forming composition SV4C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 5]
A film-forming composition (SV5) was prepared in the same manner except that S1 of Example 1 was changed to S5, and SV5 was further heated by the same method to obtain a film-forming composition SV5C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 6]
A film-forming composition (SV6) was prepared in the same manner except that S1 of Example 1 was changed to S6, and SV6 was further heated by the same method to obtain a film-forming composition SV6C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 7]
A film-forming composition (SV7) was prepared in the same manner except that S1 in Example 1 was changed to S7, and SV7 was further heated by the same method to obtain a film-forming composition SV7C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 8]
A film-forming composition (SV8) was prepared in the same manner except that S1 in Example 1 was changed to S8, and SV8 was further heated by the same method to obtain a film-forming composition SV8C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 9]
A film-forming composition (SV9) was prepared in the same manner except that S1 of Example 1 was changed to S9, and SV9 was further heated by the same method to obtain a film-forming composition SV9C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.
[Example 10]
A film-forming composition (SV10) was prepared in the same manner except that S1 of Example 1 was changed to S10, and SV10 was further heated by the same method to obtain a film-forming composition SV10C. For SV2 and SV2C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.

[Example 11]
15.00 g of T1 obtained in Synthesis Example 13 was weighed into a 20 mL eggplant-shaped flask, then 0.31 g of PGME and 0.47 g of γ-butyl lactone were added, and 3.00 g of S1 obtained in Synthesis Example 1 was added to the surface. 0.06 g of BYK-307 was added as an activator and mixed at room temperature to prepare a film-forming composition (SV11) having a solid content concentration of 50% by mass at the time of firing at 140 ° C.
The obtained SV11 was heated by the same method as described above to obtain a film-forming composition SV11C.
For SV11 and SV11C, the viscosity was measured and the coating was prepared and evaluated in the same procedure as in Example 1.

Table 1 shows the results of film thickness, refractive index, transmittance, viscosity, storage stability of viscosity, whitening, and presence / absence of cracks in Examples 1 to 11.

[Comparative Example 1]
Weigh 15.00 g of T2 obtained in Synthesis Example 14 into a 20 mL eggplant-shaped flask, then add 1.5676 g of PGME, add 3.00 g of S1 obtained in Synthesis Example 1, and solid content concentration at 140 ° C. baking. A 48% by mass film-forming composition (RV1) was prepared.
(Viscosity measurement)
The initial viscosity of RV1 was measured, and a standing test was conducted at 23 ° C. for 30 days, and the viscosity after 30 days was measured.
(Preparation and evaluation of coating)
RV1 was spin-coated on a silicon substrate at 1000 rpm for 30 seconds using a spin coater, and calcined at 80 ° C. for 1 minute and then at 230 ° C. for 5 minutes using a hot plate to obtain a film. It was tested whether whitening and cracks were visually confirmed in the film obtained on the silicon substrate. When whitening or cracks occurred, it was judged as x, and when it did not occur, it was judged as 〇.

[Comparative Example 2]
A film-forming composition (RV2) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S2, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 3]
A film-forming composition (RV3) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S3, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 4]
A film-forming composition (RV4) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S4, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 5]
A film-forming composition (RV5) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S5, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 6]
A film-forming composition (RV6) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S6, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 7]
A film-forming composition (RV7) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S7, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 8]
A film-forming composition (RV8) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S8, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 9]
A film-forming composition (RV9) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S9, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.
[Comparative Example 10]
A film-forming composition (RV10) was prepared in the same manner except that S1 of Comparative Example 1 was changed to S10, the viscosity was measured, and a film was obtained and evaluated by the same method as in Comparative Example 1.

Table 1 shows the results of viscosity, storage stability of viscosity, whitening, and presence / absence of cracks in Comparative Examples 1 to 10.

The coating film mounted on the electronic device is required to be free from whitening and cracks.
Further, the composition for forming a film is required to have no change in viscosity with time when stored at room temperature. This is because if the viscosity of the film-forming composition increases due to aging, the desired film thickness cannot be obtained, and as a result, the yield of the product decreases.

In Table 1, as shown in Examples 1 to 11, the coating film made of the coating film-forming composition of the present invention did not cause whitening or cracks even in a thick film of about 3 μm. On the other hand, in Comparative Examples 1 to 10, whitening and cracks occurred in the obtained film, and the film thickness, the refractive index, and the transmittance could not be measured.
Focusing on the storage stability of the film-forming composition evaluated by the initial viscosity and the viscosity after storage for 30 days, the viscosity of the film-forming composition of the present invention changes even when stored at 23 ° C. for 30 days. There was almost no change in viscosity even after heating, and good storage stability was shown. On the other hand, the film-forming compositions of Comparative Examples 1 to 10 had poor storage stability, such as those having a viscosity that changed with time and greatly increased during storage at 23 ° C., and some that were gelled.

Further, the films obtained in Examples 1 to 11 have a refractive index of about 1.85 at a wavelength of 550 nm, an average transmittance of 95% or more at a wavelength of 400 nm to 800 nm, and a film having a high refractive index and high transparency can be obtained. Was done.

[Consideration of binder polymer]
[Comparative Example 11]
A film-forming composition was prepared by the same method as in Example 1 except that S1 of Example 1 was changed to R1 obtained in Synthesis Example 11, but a solid was precipitated in the film-forming composition and was uniform. A film-forming composition was not obtained.

[Comparative Example 12]
A film-forming composition was prepared by the same method except that S1 of Example 1 was changed to R2 obtained in Synthesis Example 12, but a solid was precipitated in the film-forming composition, and a uniform film-forming composition was prepared. I couldn't get anything.

Comparing Examples 1 to 11 with Comparative Examples 11 and 12, it was confirmed that the polysiloxane used in Examples was suitable as the binder polymer in order to obtain a uniform film-forming composition. .. On the other hand, it was confirmed that when an acrylic polymer was selected as the binder polymer, the compatibility was poor and a uniform film-forming composition could not be obtained.

[3] Heating Conditions for Film-Forming Composition As described above, the film-forming composition of the present invention may obtain a film having a uniform film quality when it undergoes a heating step. Therefore, 10 g of the film-forming composition was weighed in a 20 mL eggplant-shaped flask, and heating steps were carried out under various heating conditions to examine the stability of the film-forming composition.

[Examples 12 to 31, Examples 32 to 36]
SV1 to SV10 were heated for 1 hour using an oil bath set at 110 ° C., 150 ° C., and 160 ° C., and the film-forming composition was observed. A uniform film-forming composition with no precipitates and no gelation was obtained in each film-forming composition.
[Comparative Examples 13 to 22]
SV1 to SV10 were heated for 1 hour using an oil bath set at 170 ° C., and the film-forming composition was observed. Needle-shaped crystal components were precipitated in each film-forming composition, and a uniform film-forming composition could not be obtained.

The results of Examples 12 to 36 and Comparative Examples 13 to 27 are shown in Table 2.
In the table, when a uniform film-forming composition was obtained, it was evaluated as ◯, and when needle-like crystals were generated and a uniform film-forming composition was not obtained, it was evaluated as x.

As shown in Table 2, in each case, the film-forming composition of the present invention did not generate needle-like crystals under heating conditions of 150 ° C. or lower, and a uniform film-forming composition was obtained. That is, it was confirmed that it is appropriate for the film-forming composition of the example to undergo a heating step under a temperature condition of 150 ° C. or lower.

However, under the heating conditions of 170 ° C., needle-like crystals were precipitated in any of the film-forming compositions, resulting in the inability to obtain a uniform film-forming composition.
When needle-like crystals are generated in the film-forming composition as in Comparative Examples 13 to 27, the dispersed state of the particles in the film-forming composition changes, and the desired film cannot be obtained. Not preferred.

Since the film-forming composition of the present invention retains a high degree of dispersibility of the inorganic fine particles, the storage stability of the film-forming composition is good and the product life is long, so that the cost can be reduced. It is possible.

Further, since a thick film is maintained, whitening and cracks do not occur, and a highly transparent film having a high refractive index can be obtained, it can be suitably used for electronic devices and optical members that require a thick film.

The film-forming composition of the present invention includes electrons such as a liquid crystal display, an organic electroluminescence (OLED) display, an optical semiconductor (LED) element, a solid-state imaging device, an organic thin film solar cell, a dye-sensitized solar cell, and an organic thin film transistor (TFT). It can be suitably used as a member when manufacturing a device. Further, it can be suitably used as a lens member for which a high refractive index is required. Embedded films and flattening films on photodiodes, flattening films before and after color filters, microlenses, flattening films and conformal films on microlenses, which are members of solid-state image sensors for which high refractive index is particularly required. Can be suitably used as.

Claims (15)

(A) Component: The following formula (1)

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
A hydrolyzate condensate of at least one hydrophilic silane represented by, and a component (B): a metal oxide colloidal particle (B1) having a primary particle diameter of 2 to 60 nm as a nucleus, and the surface thereof is 1 to 1. Poly as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating (B2) composed of metal oxide colloidal particles having a primary particle size of 4 nm. It has one or more poly (oxyalkylene) groups selected from oxyethylene group, polyoxypropylene group or polyoxybutylene group, and is selected from alkylene group or vinylene group having 1 to 18 carbon atoms as a hydrophobic group. A composition for forming a film containing inorganic fine particles to which an amphoteric organic silicon compound having one or more groups is bonded. The film-forming composition according to claim 1, wherein R ² in the formula (1) is a methyl group, an ethyl group, a phenyl group, a biphenyl group or a phenanthryl group, and a is 1. The film-forming composition according to claim 1 or 2, wherein the amphipathic organosilicon compound is a compound in which the number of moles of the oxyalkylene group added in the hydrophilic group is 3 to 40 mol. The amphoteric organic silicon compound bonded to the surface of the modified metal oxide colloidal particles (B3) of the component (B) is 0.1 with respect to the total metal oxide of the modified metal oxide colloidal particles (B3). The film-forming composition according to any one of claims 1 to 3, which is bonded at a mass ratio of about 30% by mass. The group in which the metal oxide colloidal particles (B1) of the component (B) are composed of Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce. The film-forming composition according to any one of claims 1 to 4, which is an oxide of at least one metal selected from the above. Any of claims 1 to 5, wherein the coating (B2) of the component (B) is an oxide of at least one metal selected from the group consisting of Si, Al, Sn, Zr, Mo, Sb and W. The composition for forming a film according to item 1. (A) Component: The following formula (1)

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and a is 0 to 3. It is an integer.)
Hydrolyzed condensate of at least one hydrophilic silane represented by and component (B): Metal oxide colloidal particles (B1) having a primary particle diameter of 2 to 60 nm are used as nuclei, and the surface thereof is 1 to 4 nm. Polyoxy as a hydrophilic group on the surface of modified metal oxide colloidal particles (B3) having a primary particle size of 2 to 100 nm coated with a coating (B2) composed of metal oxide colloidal particles having a primary particle size. It has one or more poly (oxyalkylene) groups selected from an ethylene group, a polyoxypropylene group or a polyoxybutylene group, and is selected from an alkylene group having 1 to 18 carbon atoms or a vinylene group as a hydrophobic group. A method for producing a film-forming composition, which comprises a step of mixing with inorganic fine particles to which an amphoteric organic silicon compound having one or more groups is bonded. The method for producing a film-forming composition according to claim 7, wherein R ² in the formula (1) is a methyl group, an ethyl group, a phenyl group, a biphenyl group or a phenanthryl group, and a is 1. The method for producing a film-forming composition according to claim 7 or 8, wherein the amphipathic organosilicon compound is a compound in which the number of moles of the oxyalkylene group added in the hydrophilic group is 3 to 40 mol. .. After the step of mixing the component (A) and the component (B),
The method for producing a film-forming composition according to any one of claims 7 to 9, which comprises a step of heating at 23 ° C. or higher and 150 ° C. or lower. A coating film obtained from the coating film-forming composition according to any one of claims 1 to 6. An electronic device comprising a base material and a coating film formed on the base material according to claim 11. An optical member including a base material and a coating film formed on the base material according to claim 11. A solid-state imaging device or charge-binding device having a complementary metal oxide semiconductor having at least one layer of the coating film according to claim 11. An embedded material, a flattening material, or a microlens material for a solid-state image sensor, comprising at least one layer of the coating film according to claim 11.